MXPA97003994A - Stabilization of organic peroxide with fosfomolibd acid - Google Patents
Stabilization of organic peroxide with fosfomolibd acidInfo
- Publication number
- MXPA97003994A MXPA97003994A MXPA/A/1997/003994A MX9703994A MXPA97003994A MX PA97003994 A MXPA97003994 A MX PA97003994A MX 9703994 A MX9703994 A MX 9703994A MX PA97003994 A MXPA97003994 A MX PA97003994A
- Authority
- MX
- Mexico
- Prior art keywords
- peroxydicarbonate
- organic peroxide
- phosphomolybdic acid
- butyl
- weight
- Prior art date
Links
- 150000001451 organic peroxides Chemical class 0.000 title claims abstract description 32
- 239000002253 acid Substances 0.000 title description 8
- 230000006641 stabilisation Effects 0.000 title description 4
- 238000011105 stabilization Methods 0.000 title description 4
- -1 peroxy compound Chemical class 0.000 claims abstract description 69
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 20
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical class O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 5
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 3
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 3
- 125000003890 2-phenylbutyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- CWINGZLCRSDKCL-UHFFFAOYSA-N ethoxycarbonyloxy ethyl carbonate Chemical compound CCOC(=O)OOC(=O)OCC CWINGZLCRSDKCL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- ZAYGISOXMIXWHX-UHFFFAOYSA-N 2-methylpropoxycarbonyloxy 2-methylpropyl carbonate Chemical compound CC(C)COC(=O)OOC(=O)OCC(C)C ZAYGISOXMIXWHX-UHFFFAOYSA-N 0.000 claims description 2
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000005394 methallyl group Chemical group 0.000 claims description 2
- 230000000979 retarding effect Effects 0.000 claims description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims 2
- CJVROGOPKLYNSX-UHFFFAOYSA-N (4-tert-butylcyclohexyl) carboxyoxy carbonate Chemical compound CC(C)(C)C1CCC(OC(=O)OOC(O)=O)CC1 CJVROGOPKLYNSX-UHFFFAOYSA-N 0.000 claims 1
- YUNUBFYYVNYKRY-UHFFFAOYSA-N carboxy hydroxy carbonate Chemical compound OOC(=O)OC(O)=O YUNUBFYYVNYKRY-UHFFFAOYSA-N 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 description 21
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 11
- VZBZCLRLPBEOBO-UHFFFAOYSA-N carboxyoxy octan-3-yl carbonate Chemical compound CCCCCC(CC)OC(=O)OOC(O)=O VZBZCLRLPBEOBO-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical group CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 229940075894 denatured ethanol Drugs 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000009965 odorless effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 235000015096 spirit Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000006069 physical mixture Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- AKUHVUBQELUSIY-UHFFFAOYSA-N butan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)C AKUHVUBQELUSIY-UHFFFAOYSA-N 0.000 description 1
- NVNPRIOOIIFZJH-UHFFFAOYSA-N carboxyoxy phenyl carbonate Chemical class OC(=O)OOC(=O)OC1=CC=CC=C1 NVNPRIOOIIFZJH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SQHSUOBKWACYNG-UHFFFAOYSA-N phenoxycarbonyloxy phenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OOC(=O)OC1=CC=CC=C1 SQHSUOBKWACYNG-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
The present invention relates to organic peroxide compositions containing phosphomolybdic acid to retard the decomposition rate of the peroxy compound
Description
STABILIZATION OF ORGANIC PEROXIDE WITH PHOSPHOMOLYBIC ACID BACKGROUND OF THE INVENTION The present invention relates to organic peroxide compositions and more specifically to peroxydicarbonate compositions, wherein phosphomolybdic acid has been added to retard the rate of decomposition of the peroxide compound. Organic peroxides such as peroxydicarbonates are useful as free radical initiators in the polymerization or copolymerization of ethylenically unsaturated monomers. For example, organic peroxides are used as initiators in the polymerase of vinyl halides, such as vinyl chloride or vinyl bromine; vinylidene halides such as vinylene chloride; and other compounds containing polymerizable unsaturated units. The products of this well known poly process have extensive commercial applications. The polymerization of vinyl halides or the copolymerization of vinyl halides with vinylidene halides is usually conducted in an aqueous medium, ie, emulsion, solution or suspension polymerization. In these polymerizations, the monomer or mixture of monomers is dispersed in water in the presence of a sulfactant and subsequently the polymerization is initiated with an organic peroxide. This is a well-known reaction that has been widely reported. All organic peroxides are by nature harmful materials. Its usefulness depends on its ability to decompose into free radicals, illustrated by the following reaction: RO-OR '? RO '+ R O' The speed of this decomposition reaction at any given temperature depends on the structure of R and R '. The decomposition reaction is exothermic. If exothermic decomposition were to occur during production, storage or shipping, when the peroxides are in a concentrated form, excessive pressure and / or fire or explosion may result. Consequently, many organic peroxides must be kept refrigerated. There have been several reports in recent years of the retardation of the decomposition rate of organic peroxides. The Journal of the American Chemical Society, Volume 72, pages 1254 to 1263 (1950), describes the use for example of ethyl acetoacetate, iodine, trinitrobenzene, acetanilide, nitromethane, phenol, hydrogen peroxide and tetralin, to retard the speed of decomposition of diisopropyl peroxydicarbonate.
The patent of the U.S.A. No. 4,515,929 (1985) reports aqueous dispersions of organic peroxides including peroxy dicarbonates, which are stabilized against decomposition by the addition of diphenyl peroxydicarbonate or di (alkyl substituted) phenyl peroxydicarbonates. The patent of the U.S.A. No. 4,552,682 (1985) describes the use of phenolic antioxidants to retard the rate of degradation of aqueous organic peroxide dispersions. The use of phenolic antioxidants is undesirable because they result in discoloration. The patent of the U.S.A. No. 5,155,192 (1992) describes the use of organic hydroperoxides, for example ter-butyl hydroperoxide, to retard the decomposition rate of peroxy dicarbonates. Research Disclosure, April 1995, on page 275, reports the thermal stabilization of dialkyl peroxydicarbonates using unsaturated nitriles or unsaturated acetylenic compounds. COMPENDIUM OF THE INVENTION The present invention relates to the use of certain non-peroxide compounds that are effective in retarding the decomposition rate of organic peroxides such as peroxydicarbonate. Thus, one aspect of the present invention is a composition containing an organic peroxide compound such as a peroxydicarbonate and phosphomolybdic acid which reduces the rate of decomposition of the peroxide compound. Another aspect of the present invention is the method of stabilizing a peroxydicarbonate against decomposition, which comprises adding phosphoric acid in an effective amount to achieve said stabilization. BRIEF DESCRIPTION DETÁt-t-Ar >; A G > The present invention relates to compositions containing an organic peroxide such as a peroxydicarbonate and phosphorandibic acid to retard the decomposition rate of the peroxide compound. Phosphomolybdic acid is a term that refers to any of the various acidic compounds of phosphorus, molybdenum, oxygen and hydrogen. Without intending to be bound by any particular molecular structure or synthesis mode, the phosphomolybdic acid can be illustrated by the formulas H3PM0-0x or H3P04-tmo07dMo02 where (which is equal to (t + d) is typically 10 to 20 but may be higher at 20 or less than 10, and x is typically 34 to 65, but may be greater than 65 or less than 34, and d may be 0. Preferred phosphomolybdic acid for use in the present invention, includes compounds corresponding to the formulas H3P 01204o ( CAS Nos. 12026-57-2 and 51429-74-4, also known as P205-20MoO3xHO), H3PM012020 (CAS Registry No. 99570-13-5) H3P 0lo034 (CAS Registry No. 99559-64-5); and H3PM0lo034 (CAS Registry No. 12519-76-5) Other phospho-olibic acids corresponding to these formulas are also contemplated within the present invention.Olhobic phosphide acid is usually associated with up to about 60 mmoles of water of hydration per mmol of water. phosphomolybdic acid. You can add Phosphomolybdic acid is in solid form but its solubility in economical solvents such as denatured ethanol, makes it practical to use phosphomolybdic acid solutions to add the desired small amounts to the organic peroxide. Other solvents useful in this aspect include other alcohols such as methanol, isopropyl alcohol, n-butanol ethers such as diethyl ethers; glycols such as ethylene glycol; ethers such as ethyl acetate; and ketone such as acetone, methyl ethyl ketone and diethyl ketone. The amount of phosphomolybdic acid for use in the compositions of the present invention is an amount sufficient to retard the rate of decomposition of the peroxide compound. The preferred amount of fssfomolybdic acid is a concentration of .001 to 1.0% and more preferably .02 to .1% by weight of the peroxydicarbonate or other organic peroxide present. When the phosphomolybdic acid is added as a solution, the amount of the solution to be used is adjusted according to the amount of phosphomolybdic acid present in the solution. The exact amount will vary and will depend on the organic peroxide compound and the conditions to which the peroxide composition is to be exposed. Peroxide compounds useful in this invention are of the general structural formula: R 1 - 0 - C (0) - O - C (0) - 0 - R2 wherein R 1 and R 2 each may be an aliphatic, cycloaliphatic or aromatic group with 1 to 22 carbon atoms, preferably 2 to 8 carbon atoms. R1 and R2 can be branched or unbranched, substituted or unsubstituted alkyl, alkenyl, cycloalkyl, or aromatic groups. Examples of groups R1 and R2 include phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, hexyl, octyl, neopentyl, 2-ethylhexyl, capryl, lauryl, myristyl, cetyl , stearyl, allyl, methallyl, crotyl, cyclohexyl, 4-t-butylcyclohexyl, 4-t-amyclohexyl, benzyl, 2-phenylethyl, 2-phenylbutyl, alpha-carbetoxyethyl, beta-methoxyethyl, 2-phenoxyethyl, 2-methoxyphenyl, 3- ethoxyphenyl, 2-ethoxyethyl, 2-ethoxyphenyl, 3-methoxybutyl, 2-carbayloxyethyl, 2-chloroethyl, 2-nitrobutyl, and 2-nitro-2-ethylpropyl. Specific examples of peroxydicarbonates include diethyl peroxydicarbonate, di-n-butyl peroxydicarbonate, di-n-butyl peroxydicarbonate, diisobutyl peroxydicarbonate, disobutilperoperoxydicarbonate and di-4-tert. < "Butylcyclohexyl peroxydicarbonate. Preferably, the peroxycarbonate is di-sec-butylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate or diisopropyl peroxydicarbonate. The peroxide compound can be symmetric or asymmetric, ie R1 and Rz may be the same or different. The peroxide may be a homogeneous mixture containing symmetric peroxides, asymmetric peroxides such as isopropyl-sec-buty1-peroxydicarbonate, or a mixture of symmetric and asymmetric peroxides such as mixtures of diisopropyl peroxydicarbonate, dl-sec-butylperoxydicarbonate and isopropyl-sec-butyl -peroxydicarbonate as described in the US patent No. 4,269,726. The peroxydicarbonate compounds can be synthesized by conventional family techniques to a person of ordinary skill in the art. Peroxydicarbonates are typically prepared by reacting the corresponding alkyl chloroformate with aqueous sodium peroxide at low temperatures, 0 to 20 ° C. The patent of the U.S.A. No. 2,370,588 and the Journal of the American Chemical Society, Volume 72, pages 1254 to 1263 (1950). Other synthetic techniques will be familiar to a person with ordinary skill in the specialty. Preferably, the peroxydicarbonates useful in this invention include those which are liquid at 0 ° C and more preferably a liquid at 5 ° C. Even more preferred are peroxydicarbonates which are liquid up to -20 ° C.
The present invention is especially applicable to aqueous dispersions of peroxydicarbonates which are useful as initiators in the polymerization of free radicals of ethylenically unsaturated materials, particularly in an aqueous medium, for example emulsion or suspension polymerization. A dispersion of the peroxydicarbonate is prepared by dispersing it in water with a convenient dispersing aid, for example a surfactant or emulsifying agent. Surfactants and emulsifying agents useful in the formation of these dispersions are well known in the art and are quite numerous. To prepare dispersions according to the present invention, the phosphomolybdic acid or a solution thereof can be added to an already formed peroxide dispersion, or to the water containing the surfactant, or to the peroxide before the dispersion is formed. Dispersions of the present invention generally contain from 20 to 70% by weight, preferably 30 to 60% by weight of the peroxydicarbonate or other organic peroxide compound and 0.001 to 1.0% (by weight of peroxide) of phosphomolybdic acid. The manner of preparation of the peroxide dispersions is known to a person of ordinary skill in the art. A description of peroxydicarbonate dispersions and their preparation can be found in U.S. Pat. No. 4,515,929; Patent of the U.S.A. Do not.
3,825,509; Patent of the U.S.A. No. 3,988,261 and U.S. Pat. No. 4,092,470. Peroxydicarbonate compositions of the present invention can also be prepared as physical mixtures in the form of liquids, granules, powders or flakes. A physical mixture according to the present invention can be prepared by mixing a liquid peroxide compound or a solution of a peroxide in a convenient solvent, with the desired amount of phosphomolybdic acid or solution thereof in a conventional mixing apparatus. The resulting mixture is then granulated, pulverized or flaked if desired. The phosphomolybdic acid can be added either (1) to the chloroformate-containing reaction mixture before preparation of the peroxide compound or (2) to the unprocessed reaction mixture immediately after preparation of the peroxide compound. Either (1) or (2) will ensure that the two components are mixed as homogeneously as possible in order to receive the greatest possible benefit from the stabilizing effect of the acid of the phosphomolybdic acid. A solution of the present invention can be prepared by combining the desired amounts of phosphomolybdic acid and peroxide in a convenient solvent. Suitable organic solvents include those normally employed for peroxydicarbonates such as esters of phthalic acid, an example of which is dibutyl phthalate and aliphatic and aromatic hydrocarbons and mixtures of these hydrocarbons, examples of which are hexane, odorless mineral spirits, mineral oil, benzene, toluene, xylene, and (iso) paraffins such as isododecane. Other suitable solvents will be familiar to a person with ordinary skill in the specialty. Solutions according to the present invention contain at least 10% and more preferably less than 25% by weight of a peroxydicarbonate compound. The peroxide compositions of the present invention exhibit numerous significant advantages. Primarily among these, improved thermal stability is provided, both in response to exposure to raising the temperature and in response to a given constant temperature. The thermal stability of self-reactive substances, in response to raising temperatures, can be determined by measuring the temperature of self-accelerating decomposition or SADT (SADT = self accelerating decomposition temperature). SADT is one of the recognized tests to determine the transport and safe storage of materials such as organic peroxides. [Transportation recommendations for dangerous goods (Reccomendations on the Transport of Dangerous Goods), ninth edition, United Nations, NY 1995, Section 11.3.5 page 264].
SADT can be correlated directly with the start temperature as measured in a differential thermal analyzer (DTA). The starting temperature is the point at which uncontrolled thermal decomposition begins. The starting temperature can be measured by determining the point at which the rate of temperature increase in a closed cell exceeds a certain pre-determined value. In addition, the start temperature can be measured by determining the point at which the rate of increase in pressure in the closed cell exceeds a certain predetermined value. Thermal stability in response to a given constant temperature can be estimated by accelerated aging tests for example at 15 ° C. Phosphomolybdic acid of the present invention increases at the starting temperature of peroxydicarbonate. Also, the phosphomolybdic acid does not impair the effectiveness of the peroxide as a polymerization initiator. The following examples are intended to illustrate the claimed invention and are in no way designed to limit its scope. Numerous additional embodiments within the scope and spirit of the claimed invention will be apparent to those skilled in the art. EXAMPLE 1 The starting temperature is measured for samples of pure di-2-ethylhexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate diluted in odorless mineral spirits (OMS) and di-sec-butyl peroxydicarbonate diluted in OMS. The starting temperature can also be measured for samples of the aforementioned peroxydicarbonates, in the presence of various amounts of phosphomolybdic acid. The liquid mixtures were prepared by dissolving the required amount of phosphomolybdic acid solution in the peroxydicarbonate. Using a type of Differential Thermal Analyzer (Radex Solo Thermal Analyzer, distributed by Astra Scientific International, Pleasanton, CA.), with an isothermal retention temperature of 30 ° C for 15 minutes and then a temperature increase of 1"/ minute to 130 ° C, the start temperature is measured for a sample of one gram of peroxydicarbonate in a closed cell.The start temperature is measured both by noting the point where the rate of increase (? T) of the sample temperature has reached 0.2 ° C / minute and also the point where the rate of increase in pressure (áP) of the closed sample cell reaches 0.0703 Kg / cm2 (1.0 psi) / minute.eltaT is the difference between the temperature of the oven and the sample temperature. P is the difference between a precalibrated reference pressure and the pressure developed in the sealed sample cell.
The results presented in Table I show that the presence of phosphomolybdic acid increases the temperature at which the self-accelerated decomposition of peroxydicarbonate will begin. This shows that phosphomolybdic acid is an effective stabilizer. Table I. Start temperature for peroxydicarbonates stabilized with phospho-bothic acid (PMA) Peroxide% by weight Temperature of PMA * pure aggregate start (° C) By AT By AP 97.7% Di-2- none 36.3 42.3 ethylhexyl-peroxydicarbonate ( pure) 97.7% Di-2- 0.1 50.2 53.9 ethylhexyl-peroxydicarbonate (pure) 74.8% Di-2- none 41.4 43.6 ethylhexyl peroxydicarbonate in WHO Table I. Starting temperature for peroxydicarbonates stabilized with phosphomolybdic acid (PMA) (Cont.)
Peroxide% by weight of Temperature of PMA * pure start added j___C By AT By AP
74. 8% Di-2- 0.62 52.6 53.5 ethylhexyl peroxydicarbonate in WHO 74.8% Dl-2- 0.2 51.5 53.5 ethylhexyl peroxydicarbonate in WHO 74.8% Dl-2- 0.1 53.9 54.2 ethylhexyl peroxydicarbonate in WHO Peroxide% wt. PMA * pure aggregate start t_c_ By AT By AP
74. 8% Di-2- 0.04 52.5 52.0 Ethylhexyl peroxydicarbonate Peroxide% by weight Temperature of PMA * pure start added! ____ By AT By AP in OMS 74.8% Di-2- 0.02 50.4 52.1 ethylhexyl peroxydicarbonate in WHO 74.8% Di -2- 0.01 47.8 47.2 ethylhexyl peroxydicarbonate in WHO 74.8% Di-2- 0.004 44.3 46.5 ethylhexyl peroxydicarbonate in WHO 74.8% Di-2- none 36.6 41.0 ethylhexyl peroxydicarbonate in WHO 74.8% Di-2-1 47.9 51.3 ethylhexyl- Peroxydicarbonate in WHO *: Added as a 20% by weight solution in denatured ethanol. EXAMPLE 2 The effect of the presence of phosphomolybdic acid on storage stability at 15 ° C of pure di-2-ethylhexyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate diluted in odorless mineral spirits (OMS) and di-sec-butylperoxydicarbonate diluted in OMS, is determined as an accelerated aging test. The purity of the peroxydicarbonate is measured at weekly intervals. The results presented in Table II show that phosphomolybdic acid is an effective stabilizer of peroxydicarbonate. Table II Purity versus time for peroxydicarbonates stabilized with phosphomolybdic acid (PMA) Peroxide% by weight% purity after pure storage PMA * added 1 week 2 weeks 3 weeks 4 weeks 97.7% Di-2- none 37.3 22.4 21.6 18.8 ethylhexyl- peroxydicarbonate (Pure) 97.7% DÍ-2- 0.1 94.7 84.0 76.7 69.4 ethylhexyl-Table II Purity against time for peroxydicarbonates stabilized with phosphomolybdic acid (PMA) Peroxide% by weight% purity after pure storage PMA * added 1 week 2 weeks 3 weeks 4 weeks peroxydicarbonate (pure) 74.8% Di-2- none 28.6 17.9 15.4 14.9 ethylhexyl peroxydicarbonate in WHO 74.8% Di-2- 0.1 70.1 64.0 57.8 53.2 ethylhexyl peroxydicarbonate in WHO Peroxide% in weight% purity after of pure storage PMA * added 1 week 2 weeks 3 weeks 4 weeks
76. 2% Di-2- none 19.9 17.7 18.2 19.4 secbutyl peroxydicarbonate in WHO Peroxide% by weight% pure after storage PMA * added 1 week 2 weeks 3 weeks 4 weeks 76.2% Di- 0.1 60.1 46.6 39.5 37.5 sec- peroxydicarbonate in WHO *: added as a 20% by weight solution in denatured ethanol.
Claims (16)
- CLAIMS 1. A composition characterized in that it comprises: (a) an organic peroxide component selected from the group consisting of peroxydicarbonate compounds and their mixtures; and (b) a sufficient amount of phosphomolybdic acid to retard the decomposition rate of the organic peroxide component.
- 2. A composition according to claim 1, characterized in that the organic peroxide component comprises at least one compound of the formula (i) R1-O-C (O) - 0-C (O) -O-R2 in where R1 and R2 independently are aliphatic, cycloaliphatic or aromatic groups containing 1 to 22 carbon atoms.
- 3. A composition according to claim 2, characterized in that R1 and R2 are independently selected from the group consisting of: phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, hexyl, octyl, neopentyl, 2-ethylhexyl, capryl, lauryl, iristyl, cetyl, stearyl, allyl, methallyl, crotyl, cyclohexyl, 4-t-butylcyclohexyl, 4-ta icliohexyl, benzyl, 2-phenylethyl, 2-phenylbutyl , alpha-carbetoxyethyl, beta-methoxyethyl, 2-phenoxyethyl, 2-methoxyphenyl, 3-methoxyphenyl, 2-ethoxyethyl, 2-ethoxyphenyl, 3-methoxybutyl, 2-carbamyloxyethyl, 2-chloroethyl, 2-nitrobutyl, and 2-nitro-2 -methylpropyl.
- 4. Composition according to claim 1, characterized in that the organic peroxide component is selected from the group consisting of: diethyl peroxydicarbonate, isopropyl-sec-butyl-but idicarbonate, di-n-butyl-peroxydicarbonate, diisobutyl peroxydicarbonate, di -4-tert-butylcyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, and mixtures thereof.
- 5. Composition according to claim 1, characterized in that the phosphomolybdic acid comprises 0.001 to 1.0% by weight of the organic peroxide component.
- 6. Compositions according to claim 5, characterized in that the phosphomolybdic acid comprises 0.02 to 0.1% by weight of the organic peroxide component.
- 7. Compositions according to claim 2, characterized in that the phosphomolybdic acid comprises 0.001 to 1.0% by weight of the organic peroxide component.
- 8. Compositions according to claim 7, characterized in that the phosphomolybdic acid comprises 0.02 to 0.1% by weight of the organic peroxide component.
- 9. Method for retarding the decomposition rate of an organic peroxide product, selected from the group consisting of peroxydicarbonate compounds and their mixtures, characterized in that it comprises adding to the organic peroxide compound phosphomolybdic acid in an amount effective to retard the rate of decomposition.
- 10. Method according to claim 9, characterized in that the peroxydicarbonate compounds correspond to the formula (I): Rx-O-C (O) -O-C (O) -O-R2 wherein R1 and R2 independently they are cycloaliphatic or aromatic aliphatic groups containing 1 to 22 carbon atoms.
- 11. Method according to claim 10, characterized in that R1 and R2 are independently selected from the group consisting of: phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl hexyl, octyl, neopentyl, 2-ethylhexyl, capryl, lauryl, iristyl, cetyl, stearyl, allyl, ratetalyl, crotyl, cyclohexyl, 4-t-butylcyclohexyl, 4-t-amylcyclohexyl, benzyl, 2-phenylethyl, 2-phenylbutyl , alpha-carbetoxyethyl, beta-methoxyethyl, 2-phenoxyethyl, 2-methoxyphenyl, 3-methoxyphenyl, 2-ethoxyethyl, 2-ethoxyphenyl, 3-ethoxybutyl, 2-carbamyloxyethyl, 2-chloroethyl, 2-nitrobutyl, and 2-nitro 2-methylpropyl.
- 12. - Method according to claim 9, characterized in that the organic peroxide component is selected from the group consisting of: diethyl peroxydicarbonate, isopropyl-sec-butyl-but-idicarbonate, di-n-buty 1-peroxydicarbonate, dissectyl peroxydicarbonate, 4-tert-butylcyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, and mixtures thereof.
- 13. Method according to claim 9, characterized in that the amount of the phosphomolybdic acid is 0.001 to 1.0% by weight of the organic peroxide product.
- 14. Method according to claim 13, characterized in that the amount of the phosphomolybdic acid is 0.02 to 0.1% by weight of the organic peroxide product.
- 15. Method according to claim 10, characterized in that the amount of the phosphomolybdic acid is 0.001 to 1.0% by weight of the organic peroxide product.
- 16. Method according to claim 15, characterized in that the amount of the phosphomolybdic acid is 0.02 to 0.1% by weight of the organic peroxide product.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/656,095 US5719304A (en) | 1996-05-31 | 1996-05-31 | Organic peroxide stabilization with phosphomolybdic acid |
| US08656095 | 1996-05-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MX9703994A MX9703994A (en) | 1998-06-30 |
| MXPA97003994A true MXPA97003994A (en) | 1998-10-30 |
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